Preparation of 2-Methylnaphthalene from 1-Methylnaphthalene Via Catalytic Isomerization and Crystallization

Available online at BCREC Website: https://bcrec.undip.ac.id

Bulletin of Chemical Reaction Engineering & Catalysis, 13 (3) 2018, 512-519

Research Article Preparation of 2-Methylnaphthalene from 1-Methylnaphthalene via Catalytic Isomerization and Crystallization

Hao Sun1*, Kang Sun1, Jianchun Jiang1, Zhenggui Gu2

1Jiangsu Key Laboratory for Biomass Energy and Material, National Engineering Laboratory for Biomass Chemical Utilization, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, China 2Jiangsu Provincial Key Laboratory of Materials Cycling and Pollution Control, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China

Received: 10th May 2018; Revised: 16th July 2018; Accepted: 17th July 2018; Available online: 14th November 2018; Published regularly: December 2018

Abstract Large amounts of residual 1-methylnaphthalene are generated when 2-methylnaphthalene is extracted from alkyl naphthalene. In order to transform waste into assets, this study proposes a feasible process for preparing 2-methylnaphthalene from 1-methylnaphthalene through isomerization and crystallization. The 1-methylnaphthalene isomerization was carried out in a fixed-bed reactor over mixed acids- treated HBEA zeolite. The results showed that acidic properties of catalysts and reaction temperature were associated with the 2-methylnaphthalene selectivity, yield and catalytic stability. At a high reaction temperature of 623 K, the 2-methylnaphthalene yield was 65.84 %, and the deactivation rate was much lower. The separation of reaction products was then investigated by two consecutive crystallization processes. Under optimal conditions, the 2-methylnaphthalene purity attained 96.67 % in the product, while the yield was 87.48 % in the refining process. Copyright © 2018 BCREC Group. All rights reserved

Keywords: Modified zeolite; 1-Methylnaphthalene, Isomerization; Crystallization; 2-Methylnaphthalene

How to Cite: Sun, H., Sun, K., Jiang, J., Gu, Z. (2018). Preparation of 2-Methylnaphthalene from 1-Methylnaphthalene via Catalytic Isomerization and Crystallization. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (3): 512-519 (doi:10.9767/bcrec.13.3.2650.512-519)

Permalink/DOI: https://doi.org/10.9767/bcrec.13.3.2650.512-519

1. Introduction oil is both inefficient and polluting, because they are made up of about 30 % alkyl naphthalenes. The production of C10 aromatics are the re- Among alkyl naphthalenes, 2-methyl- sidual oils after trimethylbenzene and indane naphthalene (2-MN) is a well-known useful in- are extracted from C9 aromatics, and have termediate for producing polyethylene naphtha- reached more than 300,000 tons per year in lene (PEN) and vitamin K [1-3]. In our previous China. Using C10 aromatics as solvents or fuel study [4], 2-MN was attained from alkyl naphthalenes via side-stream distillation and * Corresponding Author. continuous crystallization processes. However, E-mail: [email protected] (H. Sun) the residual component was mainly 1-methyl- Telp: +86-25-85482484, Fax: +86-25-85482484

Bulletin of Chemical Reaction Engineering & Catalysis, 13 (3), 2018, 513 naphthalene (1-MN), the industrial demand for Chemical Regent Co., Ltd., Shanghai, China. which is much lower than that for 2-MN. If we Parent HBEA zeolite was synthesized by the could obtain 2-MN from 1-MN, residual C10 method described in Matsukata et al. [18]. aromatics could be maximally utilized with less waste. 2.2 Catalyst Preparation Past studies [5-11] have demonstrated The parent HBEA zeolite was activated at HBEA zeolite to be an effective catalyst for 823 K (2 K/min heating rate) for 5 h before the 1-MN isomerization owing to its thermal modification. The dealuminated catalyst was stability, appropriate pore size distribution and prepared by impregnating HBEA zeolite into high activity in comparison with those of other 0.1 mol/L solution of mixed hydrochloric and zeolites. However, due to its initial defective oxalic acids (hydrochloric/oxalic = 1) at 343 K structure, detrimental by-products are una- for 1 h. After that, the sample was filtered, voidable during the synthesis process, and its washed, dried and calcined at 823 K (2 K/min catalytic life of isomerization is short. Modifica- heating rate) for 4 h. The synthesized catalyst tions of zeolites, such as: silylation [12], stream was denoted as Mix-HBEA. [13], and dealumination [14-17], are advanta- geous for improving the stability and selectivity 2.3 Characterization of catalytic reaction. Our previous report has studied the HBEA zeolite modified by organic X-ray diffraction (XRD) was recorded on a acid [11], and the modified catalyst demon- D/max-2500 (Rigaku, Japan) using Cu-Kα radi- strated high selectivity for the conversion of al- ation and operating at 100 mA and 40 kV. Fou- kyl naphthalene. Dealumination is accom- rier transform infrared (FTIR) spectroscopy plished by hydrolysis of Al–O–Si bonds with in- was conducted on a Tensor 27 (Bruker, Germa- organic and/or organic acids. It is obvious that ny) spectrometer in the mid-IR region (400- the acids used in the treatment are responsible 4000 cm-1). Surface acidity was performed with for the acidic properties and catalytic perfor- FTIR spectrometry after adsorption of pyridine mance of HBEA zeolite. Nevertheless, the mix- (Py-FTIR), using a Vertex 70 (Bruker, Germa- ture of inorganic and organic acids utilized for ny) spectrometer coupled with a conventional the dealumination of HBEA and the catalytic high vacuum system. The molar extinction co- deactivation rate of mixed acids-treated zeolite efficients for pyridine on the Brönsted (1545 for 1-MN isomerization have scarcely been in- cm-1 band, εB) and Lewis acid sites (1454 cm-1 vestigated. band, εL) were identified as 1.23 cm/μmol and The product of 1-MN isomerization contains 1.73 cm/μmol, respectively [19]. NH3 tempera- both 1-MN and 2-MN due to the thermodyna- ture-programmed desorption (NH3-TPD) was mic equilibrium of isomerization reaction. The carried out on a TP-5080 (Xianquan, China) in- components of this mixture have a large strument equipped with a thermal conductivity difference in melting point, but a small differ- detector. Thermogravimetric (TG) analysis was ence in volatility. As reported in our previous measured using a Diamond TG/DTA (Perkin study [4], crystallization is an effective method Elmer, USA) instrument in the presence of ox- for separating the isomers mixture. ygen. In order to make full use of the 1-MN resul- ting from residual C10 aromatics, this work car- 2.4 Reaction and Separation ried out the 1-MN isomerization over modified The isomerization of 1-MN was performed HBEA zeolite. The modified zeolite was charac- in a fixed-bed reactor. After 1.6 g of catalyst terized by various methods, and its catalytic was loaded in the center of the reactor, the properties were investigated in a fixed-bed re- isomerization was carried out in the presence actor. Furthermore, in order to obtain 2-MN of nitrogen under atmospheric pressure. The with high purity and yield, two-fold crystalliza- flow-rate of 1-MN and N2 were 1.3 h-1 weight tion for the separation of methylnaphthalene hourly space velocity (WHSV) and 20 mL/min, isomers was also studied. respectively. Products were sampled and ana-

lyzed at regular intervals. The 1-MN conver- 2. Materials and Methods sion was based on the 1-MN concentration 2.1 Source of Chemicals change, and 2-MN selectivity was defined as the mass ratio of 2-MN to 1-MN conversion. The 1-MN (> 98 % purity) was purchased A home-made apparatus [20] was then uti- from Aladdin Industrial Inc., Shanghai, China. lized to crystallize and filter the products of the Hydrochloric acid and oxalic acid were both isomerization reaction. This apparatus consists analytical regents obtained from Sinopharm

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of a jacketed crystallizer, a homothermal filter 3. Results and Discussion and a filtrate collector. The temperature of the 3.1 Characterization of Catalyst apparatus was controlled by a circulating pump, using cold glycol as a cooling medium. The crystal structure and lattice vibration The 2-MN yield in the crystallization process of Mix-HBEA were measured by XRD and was calculated as follows: FTIR, respectively. The XRD results plotted in Figure 1a show typical reflections of the zeolite HBEA at 7.8° and 22.5°, with no other signifi- Ycrystal .C2−MN (1) 2 − MN yield(%) = cant peaks. As shown in Figure 1b, the bands Y 2−MN at 1090 and 795 cm-1 are associated with the

symmetric and asymmetric stretching vibra- where Y2-MN is the 2-MN yield in the reaction tions of the TO4 units of zeolite, respectively. process, Ycrystal is the crystal yield of the crystal- At 569 cm-1, the adsorption band represents a lization process, and C2-MN is the 2-MN purity characteristic of the BEA framework structure of the crystal in the crystallization process. in the Mix-HBEA catalyst [21]. These results All samples were quantitatively analyzed by suggest that treatment with mixed acids pre- gas chromatography on a Trace 1300 serves the zeolite structure of HBEA. (ThermoFisher, America) using a SE-30 capil- NH3-TPD analysis was carried out to esti- lary column. A GC-MS (Varian 3800/2200) mated the types and number of acid sites on equipped with a Varian CP-Sil-19 column iden- the surface. The results are depicted in Figure tified the main components as naphthalene 2a. NH3 desorption peaks occurred in the (NA), 1-MN, 2-MN, dimethylnaphthalene ranges of 100-300 °C and 300-700 °C are as- (DMN) and polynuclear aromatic.

Figure 1. (a) XRD and (b) FTIR patterns of Mix-HBEA catalyst

Figure 2. (a) NH3-TPD curve of Mix-HBEA; (b) FTIR spectra of Mix-HBEA catalyst after desorption of pyridine at 573 K

Bulletin of Chemical Reaction Engineering & Catalysis, 13 (3), 2018, 515 cribed to weakly acidic sites and strongly acidic lower than 573 K and higher than 623 K, sites, respectively [22,23]. The amounts of weak respectively. The other reaction conditions and strong acid were calculated based on the were as follows: WHSV was 1.3 h-1, the time on areas of the two peaks, and the results are stream (TOS) was 1 h and the carrier gas flow- listed in Table 1. The amount of strong acid is rate was 20 mL/min. Table 2 lists the conver- clearly higher than that of weak acid, and these sion results over the Mix-HBEA catalyst. Like weak acid sites are unable to activate the in our previous study [11], disproportionation isomerization reaction [24]. of 1-MN to NA and DMN is observed in con- Further information on the strong Brönsted junction with the isomerization of 1-MN to and Lewis acidic properties of Mix-HBEA were 2-MN. then determined through Py-FTIR, and the re- At 573 K, the selectivity and yield of 2-MN sults are illustrated in Figure 2b. The bands at over Mix-HBEA are 96.73 % and 67.10 %, 1454 and 1545 cm-1 are related to pyridine ad- respectively. These results suggest restrained sorbed on the Lewis acid sites and Brönsted ac- disproportionation, as the 2-MN yield almost id sites, respectively [25]. The band at 1490 reaches the thermodynamic equilibrium of MN cm-1 is assigned to pyridine adsorbed on both isomers. The results of NH3-TPD and Py-FTIR Brönsted and Lewis acid sites. Therefore, the indicate that both the weak and strong Lewis amounts of Lewis and Brönsted acid sites can acid sites for Mix-HBEA are fewer in number be measured according to the absorption inten- than the strong Brönsted acid sites. These re- sities of the bands at 1454 and 1545 cm-1, sults imply that the Lewis and strong Brönsted respectively. As listed in Table 1, the ratio of acid sites in the catalyst act as active sites in strong Brönsted to Lewis acid sites was calcu- the disproportionation [28,29] and isomeriza- lated based on Figure 2b [26]. Clearly, strong tion [24,30] of 1-MN, respectively. When the re- Brönsted acid sites far outnumber the Lewis action temperature increases from 573 to 623 acid sites for Mix-HBEA. K, the conversion of 1-MN is increased to 71.98 %, while the yield of disproportionation 3.2 Catalytic Performance and Coke Formation products is slightly enhanced [8]. As a result, of Catalyst the 2-MN selectivity decreases to 91.46 %, while the yield of 2-MN remains at a high In order to investigate the conversion of level. 1-MN to 2-MN, the isomerization of 1-MN was The stability of the Mix-HBEA catalyst with performed over the Mix-HBEA catalyst at 573 TOS was also tested at 573 K and 623 K. As K and 623 K. As demonstrated by past studies shown in Figure 3a, the 1-MN conversion over [8,27], the 1-MN conversion and 2-MN selecti- Mix-HBEA decreases from 69.37 to 59.44 % af- vity are decreased distinctly at temperature

Table 1. Acidic properties of Mix-HBEA catalyst

Sample Amount of acida, mmol/g Strong B/Lb Total acid Weak acid Strong acid Mix-HBEA 0.97 0.36 0.61 3.56

a Calculated based on Figure 2a. Weak acid: The amount of weakly acid sites calculated by integrating the desorption peak in the range 150-300 °C. Strong acid: The amount of strongly acidic sites calculated by integrating the desorption peak in the range 300-700 °C. Total acid: The sum of weak and strong acid. b B/L: The ratio of strong Brönsted (B) to Lewis (L) acid site amounts calculated according to Figure 2b.

Table 2. Reaction results of 1-MN isomerization over Mix-HBEA catalyst

Reaction tem- 1-MN con- Product distributiona, wt% 2-MN Disproportionation kdb, h-1 perature, K version, wt% NA 2-MN DMN Others yield, wt% yield, wt% 573 69.37 1.02 96.73 1.45 0.80 67.10 1.72 0.017 625 71.98 3.10 91.46 4.12 1.32 65.84 5.19 0.003

Reaction conditions: WHSV: 1.3 h-1, time on stream: 1 h, carrier gas flow-rate: 20 mL/min a Main products of 1-MN conversion: naphthalene (NA), 2-methylnaphthalene (2-MN), dimethylnaphthalene (DMN), and derivatives of polynuclear aromatic hydrocarbons (others). b Deactivation rate calculated from Eq. (2).

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ter 10 h TOS at 573 K, while that is still higher tion stability of Mix-HBEA is improved signifi- than 64.56 % after 30 h at 623 K. Then, the de- cantly when the reaction temperature increas- activation rate of catalyst is estimated for the es from 573 to 623 K. Considering the 1-MN quantification of isomerization stability. As- conversion, 2-MN yield and isomerization sta- suming the adsorption equilibrium constant of bility, 623 K appears to be an appropriate reac- two MN isomers are similar, the activity decay tion temperature for 1-MN isomerization over with TOS was expressed as follows: Mix-HBEA. The slightly low reaction selective- ly is not an obstacle, as the byproducts are

ln yt - ln y0 = -kdt (2) eliminated in the crystallization process that follows. where, kd is the deactivation rate, t is the TOS, The formation of coke deposits on the used and y0 and yt represent the conversion on the catalysts was determined by TG under tempe- fresh and fouled catalyst, respectively [27]. The rature programmed oxidation, and the results

change in ln yt with TOS is plotted in Figure are shown in Figure 4. In the 40-200 °C range, 3b, and the values of kd were calculated from the weight loss is associated with adsorbed the linear fittings. As listed in Table 2, the de- moisture and gas in the catalysts. Above 200 activation rate of Mix-HBEA at 623 K is less °C, the steady weight of the fresh catalyst indi- than one fifth that at 573 K, indicating that the cates none of carbonaceous deposits in unused deactivation rate decreases with increasing re- Mix-HBEA. Nevertheless, in the 200-700 °C action temperature [31]. Thus, the isomeriza- range, the weight of the used Mix-HBEA de-

Figure 3. (a) Effects of TOS on 1-MN conversion over Mix-HBEA catalyst at 573 and 623 K; (b) Fitting of experimental points at 573 K and 623 K (reaction conditions: catalyst amount: 1.6 g, reaction pressure: 100 Kpa, WHSV: 1.3 h-1, carrier gas flow-rate: 20 mL/min)

Figure 4. TG profile of fresh Mix-HBEA and Figure 5. Effects of crystallization tempera- used Mix-HBEA catalysts after 10 h TOS at ture on 2-MN purity, 2-MN yield and crystal 573 K (heating rate: 10 °C/min, atmosphere yield (crystallization time: 180 min, filtration gas: O2, 200 mL/min) time: 20 min)

Bulletin of Chemical Reaction Engineering & Catalysis, 13 (3), 2018, 517

creases due to the oxidation of carbonaceous temperature was 261 K and the filtration time deposition in catalyst [26]. These coke deposi- was 20 min. As crystallization time increases ted on the used catalyst account for the de- from 2 to 5 h, the 2-MN purity and the yields of crease of 1-MN conversion over Mix-HBEA af- 2-MN and crystal increase distinctly. However, ter 10 h TOS at 573 K. the purity and yield of 2-MN decrease simulta- neously as the crystallization time increases 3.3 Crystallization further, despite a slight increase in crystal yield. It is indicated that the impurity can grow After the catalytic isomerization of 1-MN into the crystal lattice easily because of the over the Mix-HBEA catalyst at 623 K, crystalli- similarity of their structure with 2-MN mole- zation was carried out to refine 2-MN from the cule [34]. Therefore, 5 h represents an appro- reaction product (see Table 2). As the quality of priate crystallization time in the crystallization crystal products is remarkably influenced by process. different cooling conditions [32], the main fac- Figure 7 illustrates the effects of filtration tors including crystallization temperature, time on 2-MN purity and yields of 2-MN and crystallization time and filtration time were ex- crystal, where the crystallization temperature amined in the crystallization process. was 261 K and the crystallization time was 5 h. The effects of crystallization temperature on The crystal yield decreases as the filtration the separation process are plotted in Figure 5, time increases. Furthermore, as the filtration where crystallization and filtration times were time increases from 5 to 20 min, 2-MN purity 180 and 20 min, respectively. The crystal yield increases from 89.69 to 96.84 %, and 2-MN decreases as the crystallization temperature in- yield increases from 58.44 to 62.23 %. When creases. Meanwhile, as the crystallization tem- the filtration time increases further from 20 to perature increases from 255 to 261 K, the 2- 30 min, both 2-MN purity and yield decrease. MN purity increases from 93.61 to 95.68 %, and One possible reason for this phenomenon is the 2-MN yield also increases slightly. Howe- that several crystals might be dissolved and fil- ver, both the purity and yield of 2-MN decrease trated in the impurity [35]. Thus, an advisable as the crystallization temperature increases filtration time is 20 min. further. These results suggest that crystalliza- The above results indicate that optimal pa- tion at lower temperatures favors the nuclea- rameters for the crystallization process are as tion and growth of 2-MN crystals, whereas the follows: a crystallization temperature of 261 K, impurity would be incorporated into the gro- a crystallization time of 5 h, and a filtration wing crystals due to the burst nucleation at ex- time of 20 min. Under these conditions, the cessively low temperature [32,33]. Accordingly, 2-MN purity and yield are 96.84 % and 62.23 a crystallization temperature of 261 K is opti- %, respectively, and the crystal yield is 41.77 mal. %. Moreover, the attaining filtrate of the crys- Figure 6 illustrates the effects of crystalliza- tallization process was crystallized again under tion time on 2-MN purity and the yields of the same conditions, after which the 2-MN pu- 2-MN and crystal, where the crystallization

Figure 6. Effects of crystallization time on 2- Figure 7. Effects of filtration time on 2-MN MN purity, 2-MN yield and crystal yield purity, 2-MN yield and crystal yield (crystallization temperature: 261 K, filtration (crystallization temperature: 261 K, crystalli- time: 20 min) zation time: 5 h)

Bulletin of Chemical Reaction Engineering & Catalysis, 13 (3), 2018, 518 rity and yield are 96.25 % and 25.25 %, respec- [5] Popova, Z., Yankov, M., Dimitrov, L., Cher- tively, and the crystal yield is 17.05 %. Overall, venkov, I. (1994). Isomerization and Dispro- after two consecutive crystallization processes, portionation of 1-Methylnaphthalene on Zeo- the 2-MN purity is 96.67 % and the total 2-MN lites. React. Kinet. Catal. Lett., 52: 51-58. yield of crystallization is 87.48 %. Thus, it is [6] Fedorynska, E., Winiarek, P. (1995). Isomeri- feasible to apply isomerization and crystalliza- zation of Alkylaromatic Hydrocarbons on tion to prepare highly purified 2-MN from Nickel-Boron-Alumina Catalysts. React. 1-MN. Kinet. Catal. Lett., 54: 73-79. [7] Takagi, Y., Nobusawa, T., Suzuki, T. (1995). 4. Conclusion Prevention and Estimation of Catalytic Deac- tivation in Isomerization of 1 - In this process, the isomerization of 1-MN Methylnaphthalene. Kagaku Kogaku Ron- over the Mix-HBEA catalyst and two-fold crys- bunshu, 21: 1096-1103. tallizations to refine 2-MN were investigated. The Mix-HBEA catalyst presented fewer weak [8] Li, T.L., Liu, X.Y., Wang, X.S. (1997). Shape Selectivity for Disproportionation of Methyl- acid sites and strong Lewis acid sites than naphthalene over Zeolite Hβ. Chin. J. Catal., strong Brönsted acid sites, and it preserved the 18: 221-224. HBEA zeolite structure. At 623 K, the 2-MN yield was 65.84 % and the deactivation rate [9] Komatsu, T., Kim, J.H., Yashima, T. (1999). was 0.003 h-1 during the 1-MN isomerization MFI-type Metallosilicates as Useful Tools to Clarify What Determines the Shape Selectivi- process. After obtaining these results, the pa- ty of ZSM-5 Zeolites. ACS Symp. Ser., 738: rameters for crystallization temperature, crys- 162-180. tallization time and filtration time during the separation procedure were studied. Under opti- [10] Weitkamp, J., Neuber, M. (1991). Shape Se- mal conditions, 2-MN attained 96.67 % purity, lective Reactions of Alkylnaphthalenes in Ze- olite Catalysts. Stud. Surf. Sci. Catal., 60: and the 2-MN yield reached 87.48 % after two 291-301. consecutive crystallizations. Overall, the contri- bution of this paper lies in outlining a process [11] Sun, H., Shi, S.J., Gu, Z.G. (2017). Isomeriza- tion of Alkyl Naphthalene and Refining of 2- by which residual 1-MN from C10 aromatics can be transformed to the more valuable 2-MN. Methylnaphthalene. Chin. J. Chem. Eng., 25: 149-152.

Acknowledgments [12] Teng, H., Wang, J., Ren, X.Q., Chen, D.M. (2011). Disproportionation of Toluene by The project was supported by National Modified ZSM-5 Zeolite Catalysts with High Natural Science Foundation of China Shape-selectivity Prepared using Chemical (31770629) and National Nonprofit Institute Liquid Deposition with Tetraethyl Orthosili- Research Grant of CAFINT cate. Chin. J. Chem. Eng., 19: 292-298. (CAFYBB2017SY031). [13] Zhang, C., Guo, X.W., Song, C.S., Zhao, S.Q., Wang, X.S. (2010). Effects of Steam and TE- References OS Modification on HZSM-5 Zeolite for 2,6- Dimethylnaphthalene Synthesis by Methyla- [1] Pu, S.B., Inui, T. (1996). Synthesis of 2,6- tion of 2-Methylnaphthalene with Methanol. Dimethylnaphthalene by Methylation of Me- Catal. Today, 149: 196-201. thylnaphthalene on Various Medium and Large-pore Zeolite Catalysts. Appl. Catal. A, [14] Bai, G.Y., Han, J., Zhang, H.H., Liu, C., Lan, 146: 305-306. X.W., Tian, F., Zhao, Z., Jin, H. (2014). Friedel–Crafts Acylation of Anisole with Oc- [2] Lillwitz, L.D. (2001). Production of Dimethyl- tanoic Acid over Acid Modified Zeolites. RSC 2,6-naphthalenedicarboxylate: Precursor to Adv., 4: 27116-27121. Polyethylene Naphthalene. Appl. Catal. A, 221: 337-358. [15] Chen, Z.H., Feng, Y.F., Tong, T.X., Zeng, A.W. (2014). Effects of Acid-modified HBEA [3] Arkhireyeva, A., Hashemi, S. (2001). Fracture Zeolites on Thiophene Acylation and the Behaviour of Polyethylene Naphthalene Origin of Deactivation of Zeolites. Appl. (PEN). Polymer, 43: 289-300. Catal. A, 482: 92-98. [4] Sun, H., Jiang, L., Gu, Z.G. (2015). Extract [16] Bai, G.Y., Zhang, H.H., Li, T.Y., Dong, H.X., Methylnaphthalene from C10 Aromatics with Han, J. (2014). Friedel–Crafts Acylation of Sidetrack Distillation and Continuous Crys- Anisole with Hexanoic Acid Catalyzed by Hβ tallisation. Mater. Res. Innovations, 19: 573- Zeolite-supported Tungstophosphoric Acid. 578. Res. Chem. Intermed., 41: 5041-5048.

Bulletin of Chemical Reaction Engineering & Catalysis, 13 (3), 2018, 519

[17] Srivastava, R., Iwasa, N., Fujita, S., Arai, M. [27] Rombi, E., Monaci, R., Solinas, V. (1999). Ki- (2009). Dealumination of Zeolite Beta Cata- netics of Catalyst Deactivation. An Example: lyst under Controlled Conditions for Enhanc- Methylnaphthalene Transformation. Catal. ing Its Activity in Acylation and Esterifica- Today, 52: 321-330. tion. Catal. Lett., 130: 655-663. [28] Cañizares, P., Carrero, A. (2003). Dealumina- [18] Matsukata, M., Ogura, M., Osaki, T., Rao, tion of Ferrierite by Ammonium Hexafluoro- P.R.H.P., Nomura, M., Kikuchi, E. (1999). silicate Treatment: Characterization and Conversion of Dry Gel to Microporous Crys- Testing in the Skeletal Isomerization of n- tals in Gas Phase. Top. Catal., 9: 77-92. Butene. Appl. Catal. A, 248: 227-237. [19] Tamura, M., Shimizu, K.I., Satsuma, A. [29] Wang, Y., Otomo, R., Tatsumi, T., Yokoi, T. (2012). Comprehensive IR Study on Acid/Base (2016). Dealumination of Organic Structure- Properties of Metal Oxides. Appl. Catal. A, Directing Agent (OSDA) Free Beta Zeolite for 433-434: 135-145. Enhancing Its Catalytic Performance in n- Hexane Cracking. Microp. Mesop. Mater., [20] Gu, Z.G., Jiang, L. (2013). A Integrated Sepa- 220: 275-281. ration Apparatus Including Homothermal Crystallization and Filtration. CN 202682829 [30] Kumsapaya, C., Bobuatong, K., Khongpra- U (in Chinese). cha, P., Tantirungrotechai, Y., Limtrakul, J. (2009). Mechanistic Investigation on 1,5- to [21] Saxena, S.K., Viswanadham, N., Sharma, T. 2,6-Dimethylnaphthalene Isomerization Cat- (2014). Breakthrough Mesopore Creation in alyzed by Acidic β Zeolite: ONIOM Study BEA and Its Enhanced Catalytic Performance with an M06-L Functional. J. Phys. Chem. C, in Solvent-free Liquid Phase Tert-butylation 113: 16128-16137. of Phenol. J. Mater. Chem. A., 2: 2487-2490. [31] Guisnet, M., Costa, L., Ribeiro, F.R. (2009). [22] Esquivel, D., Cruz-Cabeza, A.J., Jiménez- Prevention of Zeolite Deactivation by Coking. Sanchidrián, C., Romero-Salguero, F.J. J. Mol. Catal. A: Chem., 305: 69-83. (2011). Enhanced Concentration of Medium Strength Brönsted Acid Sites in Aluminium- [32] Ye, C.P., Ding, X.X., Li, W.Y., Mu, H., Wang, modified β Zeolite. Catal. Lett., 142: 112-117. W., Feng, J. (2018). Determination of Crystal- line Thermodynamics and Behavior of An- [23] Jin, D.F., Zhu, B., Hou, Z.Y., Fei, J.H., Lou, thracene in Different Solvents. AIChE J., 64: H., Zheng, X.M. (2007). Dimethyl Ether Syn- 2160-2167. thesis via Methanol and Syngas over Rare Earth Metals Modified Zeolite Y and Dual [33] Ye, C.P., Zheng, H., Wu, T.T., Fan, M.M., Cu–Mn–Zn Catalysts. Fuel, 86: 2707-2713. Feng, J., Li, W.Y. (2014). Optimization of Sol- vent Crystallization Process in Obtaining [24] Wang, Y.L., Xu, L., Yu, Z.X., Zhang, X.Z., Liu, High Purity Anthracene and Carbazole from Z.M. (2008). Selective Alkylation of Naphtha- Crude Anthracene. AIChE J., 60: 275-281. lene with Tert-Butyl Alcohol over HY Zeolites Modified with Acid and Alkali. Catal. Com- [34] Liu, J., Chang, Z.D., Sun, X.H., Shen, S.F., mun., 9: 1982-1986. Lei, C., Liu, H.Z. (2006). Impurity Effects on the Crystallization of Avermectin B1a. J. [25] Marques, J.P., Gener, I., Ayrault, P., Bordado, Cryst. Growth, 291: 448-454. J.C., Lopes, J.M., Ribeiro, F.R., Guisnet, M. (2003). Infrared Spectroscopic Study of the [35] Cisternas, L.A., Vásquez, C.M., Swaney, R.E. Acid Properties of Dealuminated BEA Zeo- (2006). On the Design of Crystallization- lites. Microp. Mesop. Mater., 60: 251-262. based Separation Processes: Review and Ex- tension. AIChE J., 52: 1754-1769. [26] Decolatti, H.P., Costa, B.O.D., Querini, C.A. (2015). Dehydration of Glycerol to Acrolein using H-ZSM5 Zeolite Modified by Alkali Treatment with NaOH. Microp. Mesop. Ma- ter., 204: 180-189.